CN102372542A - Method for improving yield of ethylene and propylene - Google Patents
Method for improving yield of ethylene and propylene Download PDFInfo
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- CN102372542A CN102372542A CN2010102620176A CN201010262017A CN102372542A CN 102372542 A CN102372542 A CN 102372542A CN 2010102620176 A CN2010102620176 A CN 2010102620176A CN 201010262017 A CN201010262017 A CN 201010262017A CN 102372542 A CN102372542 A CN 102372542A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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Abstract
The invention relates to a method for improving the yield of ethylene and propylene, and mainly solves the problem that the yield of the ethylene and the propylene is lower in the prior art. The problem is better solved by adopting the technical scheme that the method comprises the following steps that: (1) a raw material which mainly comprises methanol enters a reaction zone at the gas-phase linear velocity of between 1.0 and 3.0m/s, and is contacted with a catalyst comprising an aluminosilicophosphate molecular sieve to generate product material flow comprising the ethylene and the propylene and form a spent catalyst at the same time; (2) the spent catalyst is at least divided into two parts, one part returns to the reaction zone, and the other part enters a regenerator for regeneration so as to form a regenerated catalyst with the activity index of more than 0.7; and (3) the regenerated catalyst is degassed and then enters the reaction zone between one-third height and four-fifth height, and the transformation rate of the methanol at the height is over 30 percent. The method can be used for the industrial production of the ethylene and the propylene.
Description
Technical field
The present invention relates to a kind of method that improves ethene, propene yield.
Background technology
Low-carbon alkene, promptly ethene and propylene are two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are to produce through petroleum path, but because limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people begin to greatly develop the technology that alternative materials transforms system ethene, propylene.Wherein, One type of important alternative materials that is used for low-carbon alkene production is an oxygenatedchemicals; For example alcohols (methyl alcohol, ethanol), ethers (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed through coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, like methyl alcohol, can be made by coal or Sweet natural gas, and technology is very ripe, can realize up to a million tonnes industrial scale.Because the popularity in oxygenatedchemicals source is added and is transformed the economy that generates low-carbon alkene technology, so by the technology of oxygen-containing compound conversion to produce olefine (OTO), particularly the technology by methanol conversion system alkene (MTO) receives increasing attention.
In US 4499327 patents silicoaluminophosphamolecular molecular sieves catalyst applications is studied in great detail in methanol conversion system olefin process, think that SAPO-34 is the first-selected catalyzer of MTO technology.The SAPO-34 catalyzer has very high selectivity of light olefin, and activity is also higher, and can make methanol conversion is the degree that was less than in reaction times of low-carbon alkene 10 seconds, more even reach in the reaction time range of riser tube.
Announced among the US 6166282 that a kind of methanol conversion is the technology and the reactor drum of low-carbon alkene; Adopt fast fluidized bed reactor; Gas phase is after the lower Mi Xiangfanyingqu reaction of gas speed is accomplished; After rising to the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Because reaction after product gas and catalyzer sharp separation have effectively prevented the generation of secondary reaction.Through analog calculation, to compare with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyzer all significantly reduce.But yield of light olefins is general all about 77% in this method, has the lower problem of yield of light olefins.
Announced among the CN 1723262 that it is low-carbon alkene technology that the multiple riser reaction unit that has central catalyst return is used for oxygenate conversion; This covering device comprises a plurality of riser reactors, gas solid separation district, a plurality of offset components etc.; Each riser reactor has the port of injecting catalyst separately; Be pooled to the disengaging zone of setting, catalyzer and product gas are separated.Yield of light olefins is general all between 75～80% in this method, has the lower problem of yield of light olefins equally.
Prior art still exists ethene, shortcoming that propene yield is lower, and the present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the lower problem of ethene, propene yield that exists in the prior art, and a kind of new raising ethene, the method for propene yield are provided.This method is used for the production of ethene, propylene, has yield of light olefins advantage of higher in the product.
For addressing the above problem; The technical scheme that the present invention adopts is following: a kind of method that improves ethene, propene yield; May further comprise the steps: the raw material entering gas phase linear speed that (1) is mainly methyl alcohol is the reaction zone of 1.0～3.0 meter per seconds; Contact with the catalyzer that comprises silicoaluminophosphamolecular molecular sieve, generate the product stream that comprises ethene, propylene, form reclaimable catalyst simultaneously; (2) said reclaimable catalyst is divided into two portions at least, and a part is returned said reaction zone, and a part gets into revivifier regeneration, forms activity index greater than 0.7 regenerated catalyst; (3) said regenerated catalyst gets into 1/3～4/5 reaction zone height place after outgasing, and the methanol conversion at this place is greater than 30%.
In the technique scheme, said silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-18, the SAPO-34, and preferred version is selected from SAPO-34; The reaction conditions of said reaction zone is: it is that the average coke content of catalyzer in 400～500 ℃, said reaction zone is 1.5～35% weight that reaction pressure is counted 0.01～0.3MPa, reaction zone medial temperature with gauge pressure; 20～50% districts revivifier regeneration of said reclaimable catalyst, 50～80% return reaction zone; Said regenerated catalyst gets into 1/2～4/5 reaction zone height place after outgasing, the methanol conversion at this place is greater than 50%; The activity index of said regenerated catalyst is greater than 0.8.
The method of calculation of coke content according to the invention are that carbon deposit quality on the catalyzer of certain mass is divided by described catalyst quality.Carbon deposit measuring method on the catalyzer is following: will mix the catalyst mix that has carbon deposit comparatively uniformly; The accurate carbon-bearing catalyzer of weighing certain mass then; Be put in the pyrocarbon analyser and burn; Through the carbonic acid gas quality of infrared analysis burning generation, thereby obtain the carbonaceous amount on the catalyzer.
The regenerated catalyst activity index is used to embody the regeneration level of decaying catalyst; With the live catalyst is benchmark; The amount that transforms methyl alcohol with each catalyzer under the rigid condition is carried out relatively, and method of calculation are: regenerated catalyst activity index=(quantity of methyl alcohol that live catalyst transforms under quantity of methyl alcohol/certain condition that regenerated catalyst transforms under the certain condition) * 100%.
Known in the field, be in the reaction process of low-carbon alkene in methanol conversion, a certain amount of carbon distribution of accumulation helps improving the selectivity of low-carbon alkene on the catalyzer.Adopt method of the present invention, regenerated catalyst is back to reaction zone 1/3～4/5 highly locates, guarantee that the methanol feeding grid distributor is to the space of regenerated catalyst in-position; Methanol feedstock contacts with the reclaimable catalyst that returns; Because the reclaimable catalyst carbon deposition quantity is higher, so the selectivity of low-carbon alkene is higher, after the intact part of methanol conversion; Upwards contact, transformed methanol feedstock with highly active regenerated catalyst.This method effectively raises the selectivity of light olefin in the methanol-to-olefins reaction process, has guaranteed the high conversion of methyl alcohol again simultaneously, thereby reaches the purpose that improves yield of light olefins.
Adopt technical scheme of the present invention: said silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-18, the SAPO-34; The reaction conditions of said reaction zone is: it is that the average coke content of catalyzer in 400～500 ℃, said reaction zone is 1.5～3.5% weight that reaction pressure is counted 0.01～0.3MPa, reaction zone medial temperature with gauge pressure; 20～50% districts revivifier regeneration of said reclaimable catalyst, 50～80% return reaction zone; Said regenerated catalyst gets into 1/2～4/5 reaction zone height place after outgasing, the methanol conversion at this place is greater than 50%; The activity index of said regenerated catalyst is greater than 0.8, and low-carbon alkene carbon back yield can reach 83.58% weight, and is higher more than 3% than low-carbon alkene carbon back yield of the prior art, obtained better technical effect.
Description of drawings
Fig. 1 is the schematic flow sheet of scheme according to the invention.
Among Fig. 1,1 is the raw material charging; 2 is reaction zone; 3 are gas-solid sharp separation equipment; 4 is stripping zone; 5 is reclaimable catalyst circulation inclined tube; 6 is inclined tube to be generated; 7 is interchanger; 8 is gas-solid cyclone separator; 9 is the reactor drum disengaging zone; 10 is the product collection chamber; 11 is the product gas outlet pipeline; 12 is regenerator sloped tube.
Methanol feedstock gets in the reaction zone 2 through feeding line 1; Contact with sieve catalyst; Reaction generates the product that contains ethene, propylene, carries reclaimable catalyst and gets into reactor drum disengaging zone 9 through gas-solid sharp separation equipment 3, wherein; Most of catalyzer that gas-solid sharp separation equipment 3 is separated gets into stripping zone 4; And gaseous products and part are not separated through going into cyclonic separator 8 by gas-solid sharp separation equipment 3 isolating catalyzer once more, and catalyzer turns back to stripping zone 4 through the dipleg of cyclonic separator 8, and gaseous products gets into collection chamber 10 after outlet line 11 gets into follow-up centrifugal station.At least be divided into two portions by gas-solid sharp separation equipment 3 and cyclonic separator 8 isolated reclaimable catalysts through behind the stripping; A part is through turning back to the bottom of reaction zone 2 through catalyst recirculation inclined tube 5 after interchanger 7 heat exchange; A part gets into coke-burning regeneration in the revivifier through inclined tube 6 to be generated in addition, and the catalyzer that regeneration is accomplished returns in the reaction zone 2 through regenerator sloped tube 12.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
In small-sized fast fluidized bed reaction regeneration device, the same Fig. 1 of reactor drum pattern.The reaction zone medial temperature is 500 ℃, and reaction pressure is counted 0.1MPa with gauge pressure, pure methanol feeding; Catalyst type is seen table 1; Stripping zone stripping medium is a water vapour, and the gas superficial linear speed in the reaction zone is 1.5 meter per seconds, and the average coke content of the catalyzer in the reaction zone is 2.8% weight.Reclaimable catalyst is divided into two portions, and 40% goes revivifier regeneration, and 60% returns the reaction zone bottom; The regenerated catalyst activity index is 0.87, and regenerated catalyst gets into 1/2 reaction zone height place of reaction zone, through sampling analysis; The methanol conversion at this place is 68%; Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and reaction result is seen table 1.
Table 1
| Parameter | Catalyst type | Low-carbon alkene carbon back yield, % weight |
| Embodiment 1 | SAPO-18 | 80.27 |
| |
SAPO-34 | 82.79 |
[embodiment 3～4]
According to embodiment 2 described condition and steps, just change the reaction zone medial temperature, reaction result is seen table 2.
Table 2
| Parameter | The reaction zone medial temperature, ℃ | Low-carbon alkene carbon back yield, % |
| Embodiment | ||
| 3 | 400 | 79.73 |
| |
470 | 83.16 |
[embodiment 5～6]
According to embodiment 2 described condition and steps, just change reaction pressure and gaseous line speed, reaction result is seen table 3.
Table 3
[embodiment 7]
According to embodiment 2 described condition and steps, changing the regenerated catalyst activity index is 0.71, and regenerated catalyst gets into 4/5 reaction zone height place of reaction zone; Through sampling analysis, the methanol conversion at this place is 81%, and reclaimable catalyst is divided into three parts; Wherein 20% go revivifier regeneration; Remaining 80% is equally divided into two portions, returns the reaction zone bottom through the catalyst recirculation pipe, and the average coke content of the catalyzer in the reaction zone is 2.5% weight; The reactor outlet product adopts online gas chromatographic analysis, and low-carbon alkene carbon back yield is 83.58% (weight).
[embodiment 8]
According to embodiment 2 described condition and steps, the reaction zone medial temperature is 425 ℃, and the average carbon deposition quantity of catalyzer is 3.5%; Changing the regenerated catalyst activity index is 0.94, and regenerated catalyst gets into 1/3 reaction zone height place of reaction zone, through sampling analysis; The methanol conversion at this place is 31%, and reclaimable catalyst is divided into three parts, wherein 50% goes revivifier regeneration; Remaining 50% is equally divided into two portions; Return the reaction zone bottom through the catalyst recirculation pipe, the reactor outlet product adopts online gas chromatographic analysis, and low-carbon alkene carbon back yield is 80.08% (weight).
[embodiment 9]
According to embodiment 2 described condition and steps, the reaction zone medial temperature is 450 ℃, and the average carbon deposition quantity of catalyzer is 1.5%; Changing the regenerated catalyst activity index is 0.8, and regenerated catalyst gets into 3/5 reaction zone height place of reaction zone, through sampling analysis; The methanol conversion at this place is 63%; Reclaimable catalyst is divided into two portions, wherein 70% goes revivifier regeneration, and 30% returns the reaction zone bottom; The reactor outlet product adopts online gas chromatographic analysis, and low-carbon alkene carbon back yield is 78.85% (weight).
[comparative example 1]
According to embodiment 2 described condition and steps, just regenerated catalyst directly returns the reaction zone bottom through regenerator sloped tube, and the low-carbon alkene carbon back yield of reactor outlet is 80.87% (weight).
Obviously, adopt method of the present invention, can reach the purpose that improves ethene, propylene carbon back yield, have bigger technical superiority, can be used in the industrial production of ethene, propylene.
Claims (7)
1. method that improves ethene, propene yield may further comprise the steps:
(1) it is the reaction zone of 1.0～3.0 meter per seconds that the raw material that is mainly methyl alcohol gets into the gas phase linear speed, contact with the catalyzer that comprises silicoaluminophosphamolecular molecular sieve, and generation comprises the product stream of ethene, propylene, forms reclaimable catalyst simultaneously;
(2) said reclaimable catalyst is divided into two portions at least, and a part is returned said reaction zone, and a part gets into revivifier regeneration, forms activity index greater than 0.7 regenerated catalyst;
(3) said regenerated catalyst gets into 1/3～4/5 reaction zone height place after outgasing, and the methanol conversion at this place is greater than 30%.
2. according to the method for the said raising ethene of claim 1, propene yield, it is characterized in that said silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-18, the SAPO-34.
3. according to the method for the said raising ethene of claim 2, propene yield, it is characterized in that said silicoaluminophosphamolecular molecular sieve is selected from SAPO-34.
4. according to the method for the said raising ethene of claim 1, propene yield, it is characterized in that the reaction conditions of said reaction zone is: it is that the average coke content of catalyzer in 400～500 ℃, said reaction zone is 1.5～3.5% weight that reaction pressure is counted 0.01～0.3MPa, reaction zone medial temperature with gauge pressure.
5. according to the method for the said raising ethene of claim 1, propene yield, it is characterized in that 20～50% districts revivifier regeneration of said reclaimable catalyst, 50～80% return reaction zone.
6. according to the method for the said raising ethene of claim 1, propene yield, it is characterized in that said regenerated catalyst gets into 1/2～4/5 reaction zone height place after outgasing, the methanol conversion at this place is greater than 50%.
7. according to the method for the said raising ethene of claim 1, propene yield, the activity index that it is characterized in that said regenerated catalyst is greater than 0.8.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772092A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Reaction device for converting methanol into light olefin |
| CN113387765A (en) * | 2020-03-13 | 2021-09-14 | 中国石油化工股份有限公司 | Method for preparing olefin by using methanol as raw material |
| CN113385113A (en) * | 2020-03-13 | 2021-09-14 | 中国石油化工股份有限公司 | Method for improving yield of ethylene and propylene and fluidized bed reactor |
| CN113457586A (en) * | 2021-07-05 | 2021-10-01 | 中国石油化工股份有限公司 | External heating fluidized bed reactor and method for carbon monoxide isothermal transformation |
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| CN101279876A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for preparing ethylene and propone with oxocompound |
| CN101318870A (en) * | 2008-06-12 | 2008-12-10 | 中国石油化工股份有限公司 | Process for improving yield of ethylene and propylene |
| CN101357874A (en) * | 2008-06-12 | 2009-02-04 | 中国石油化工股份有限公司 | Method for producing low carbon olefinic hydrocarbon from methanol or dimethyl ether |
-
2010
- 2010-08-23 CN CN2010102620176A patent/CN102372542A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279876A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for preparing ethylene and propone with oxocompound |
| CN101318870A (en) * | 2008-06-12 | 2008-12-10 | 中国石油化工股份有限公司 | Process for improving yield of ethylene and propylene |
| CN101357874A (en) * | 2008-06-12 | 2009-02-04 | 中国石油化工股份有限公司 | Method for producing low carbon olefinic hydrocarbon from methanol or dimethyl ether |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772092A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Reaction device for converting methanol into light olefin |
| CN113387765A (en) * | 2020-03-13 | 2021-09-14 | 中国石油化工股份有限公司 | Method for preparing olefin by using methanol as raw material |
| CN113385113A (en) * | 2020-03-13 | 2021-09-14 | 中国石油化工股份有限公司 | Method for improving yield of ethylene and propylene and fluidized bed reactor |
| CN113457586A (en) * | 2021-07-05 | 2021-10-01 | 中国石油化工股份有限公司 | External heating fluidized bed reactor and method for carbon monoxide isothermal transformation |
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Application publication date: 20120314 |